Detergent composition



United States Patent 3,332,876 DETERGENT COMPOSITION Arthur Pold'enWalker, Whitley Bay, England, assignor to The Procter & Gamble Company,Cincinnati, Ohio, a corporation of Ohio NoDrawing. Continuation ofapplication Ser. No.

423,298, Jan. 4, 1965. This application June 29,

1966, Ser. No. 561,374

Claims. (Cl. 252-152) This application is a continuation of Ser. No.423,298, filed Jan. 4, 1965, by Arthur Polden Walker, entitled,

Detergent Composition.

This invention relates to detergent compositions having outstandingsudsing and detergent properties, based on synergistic ternary mixturesof olefin sulfonates, alkyl benzene sulfonates and alkyl ether sulfates.

Mixtures of alkyl benzene sulfonates and alkyl ethylene glycol orpolyethylene glycol ether sulfates have previously been used incombination detergent compositions and have synergistic properties. Thusthe detergent power and sudsing power of mixtures of these detergentsare I greater than would be expected from consideration of theirperformance when used alone.

It is also known that olefins having a free hydrogen atom on a carbon inthe alpha-position can be sulfonated directly using vigorous sulfonatingagents. The sulfo radical attaches to the terminal carbon atom and thedouble bond remains intact, but may migrate from the alpha position.When the olefins have suitable molecular weight,

the sulfonates have detergent properties.

It has now been found that ternary mixtures of olefin sulfonates, alkylaryl sulfonates and alkyl ether sulfates are synergistic, and havesudsing and cleaning power better than would be expected from aknowledge of their performance when used alone, and, in particular,better than would be expected from a knowledge of the performance ofbinary mixtures, especially mixtures of alkyl benzene sulfonates andalkyl ether sulfates, without the third component, and of the thirdcomponent alone.

According to the invention therefore there is provided a detergentcomposition comprising a synergistic ternary mixture of (A) an olefinsulfonate having 12 to 16 carbon atoms in the molecule, (B) an alkylbenzene sulfonate having an alkyl chain containing 10 to 18 carbon atomsand (C) an alkyl ether sulfate having the formula RO(C H O),,SO Mwherein R is an alkyl chain having 10 to 18 carbon atoms, x is l to 5,and M is a cation.

The term olefin sulfonates is used herein to mean compounds which can beproduced by the sulfonation of alpha olefins by means of uncomplexedsulfur trioxide, followed by neutralization of the acid reaction mixturein conditions such that any sultones which have .been formed in thereaction are hydrolysed to give the preferably 12 to 14 carbon atoms.Preferably, they are straight chain olefins. Olefin sulfonates havingmore than 16 carbon atoms do not give the desired high latheringperformance in the mixtures according to the invention; those with fewerthan 12 carbon atoms having reduced detergent properties.

In addition to the true alkene sulfonates and a proportion ofhydroxy-alkane sulfonates, the olefin sulfonates 3,332,876 Patented July25, 1967 ice may contain minor amounts of other materials, arising fromimpurities in the original olefin stock and from side reactions duringthe sulfonation process.

A preferred embodiment of the present invention is the use herein of theolefin sulfonate compositions which are described completely in a patentapplication Ser. No. 516,139, filed Dec. 23, 1965, by Phillip F.Pflaumer and Adriaan Kessler and titled, Detergent Composition.

The alkyl aryl sulfonates are preferably alkyl benzene sulfonates, andthe alkyl chain preferably has 12 to 16 carbon atoms. The alkyl chainmay be derived, for example, from branched or straight chain olefins,such as tetraor penta-propylene polymers or mixtures thereof, straightchain alpha-olefins obtained from petroleum cracking or by thepolymerization of ethylene, or from halogenated paraffins. An alkylchain which is a straight chain containing 12 carbon atoms is generallyvery suitable.

The alkyl ether sulfates can be made by the condensation by knownmethods of ethylene oxides on to monohydric alcohols having 10 to 18carbon atoms. Preferably, R has 12 to 14 carbon atoms. The alcohols maybe derived from fats, e.g., coconut oil, or they may be synthetic.Lauryl alcohol and straight chain alcohols derived from coconut oil arepreferred. Such alcohols are reacted with 1 to 5, and especially 3,molar proportions of ethylene oxide and the resulting mixture ofmolecular species, having, for example, an average of 3 moles ofethylene oxide per mole of alcohol, is sulfated and neutralized.

The cation in the case of all the detergent ingredients may be alkalimetal, ammonium or a substituted ammonium radical, or (as furtherexplained below) may be in part magnesium, or may be an alkaline earthmetal. It may be a mixture of any two or more of these.

While the addition of even small amounts of the olefin sulfonates to anymixtures of the alkyl aryl sulfonates and the alkyl ether sulfatesprovides synergistic. mixtures, preferred mixtures comprise 5 to of theolefin sulfonate, by weight of the ternary mixture and to 25% of amixture comprising the alkyl aryl sulfonate and the alkyl ether sulfatein a ratio from 9:1 to 3:7 by Weight. Especially good performance isgiven by ternary mixtures containing 5 to 50% of the olefin sulfonate,and 95 to 50% of a mixture of the alkyl aryl sulfonate and the alkylether sulfate in a ratio of from 8.5 :15 to 1:1 by Weight.

It is found that the synergistic properties of the ternary mixtures ofthe invention are most marked when the compositions are used in hardwater. Accordingly, where they may be used in soft water, it isadvantageous to include some of a source of water hardness in thecomposition. This may be done by including a source of magnesium ion inthe composition, either by adding a soluble magnesium salt, such as thesulfate or chloride or by incorporating one of the detergent ingredientsat least partly in the form of its magnesium salt.

The compositions may contain any of the other ingredients usual indetergent compositions such as alkaline builder salts, bleaches, opticalbrighteners, sequestering agents, soil suspending agents, colors,perfumes, bacteriocides and the like. Other organic detergents may bepresent in minor proportions provided that they do not impair theperformance of the ternary mixture of the invention. In particular,lather stabilizers, while usually unnecessary, may be added; examplesare fatty acyl ethanolamides, especially lauric monoethanolamide.

The ternary mixtures are useful in solid, pasty or liquid detergentcompositions, and are particularly well suited to liquid ones. In suchliquid compositions they are dispersed or dissolved in a liquid medium,preferably water, optionally containing solubilizing agents such aslower monohy'dric alcohols having 1 to 4 carbon atoms, or hydrotropicsalts such as toluene or xylene sulfonates, etc.

The following examples serve to illustrate the invention. In theseexamples, the latherin'g power of the detergent compositions wasmeasured by the following test.

A frame was provided in which a number, for example six, 500 ml.cylinders could be placed and rotated about an axis perpendicular totheir long axis. Into each cylinder was placed 100' ml. of a solution ofthe detergent composition in water at 115 F., the concentration beingselected according to the information required from the test. To eachsolution was added 3 ml. of a standard soil load, namely, a liquidedible shortening based mainly on marine oils. The cylinders were thenrotated in the frame for 1 minute at 20 r.p.m. They were then stoodupright, the stoppers were removed, and the lather height above theclear liquid was measured. A further addition of 3 ml. of the soil wasmade and the procedure was repeated until substantially no latherremained.

The sum of the measured lather heights is reported as the lather height.

Example I Several diflerent liquid detergent compositions were made,each containing a total of 40% by weight of active detergent consistingof olefin sulfonates derived from alpha-olefin having 14 carbon atoms,tetra-propylene alkyl benzene sulfonate, and coconut alkyl trie-thyleneglycol ether sulfate, all in the form of their sodium salts. Theproportions of these components in each composition are indicated in thetable below. The remainder of each composition consisted primarily ofwater, containing sufficient solubilizing agent (lower alcohol and, ifnecessary, hydrotrope) to give a homogeneous composition. Eachcomposition was dissolved in hard water (18) to give a solutioncontaining 0.26% of the composition, and tested for lather power by themethod described above. The results are given in the following table:

Composition Olefin Lather Serial Snltonate Height Alkyl benzene Alkylether (Inches) sulfonate Sulfate Compositions f and g were according tothe invention, the others being .included for comparison. Composition 1had better lather power than the best binary mixtures e. Composition ghad better lather power than would be expected of a 1:1 mixture of halfthe detergent ingredients of compositions a and d, which would have thesame formula.

The compositions according to the invention had excellent detergentproperties.

Example II Composition Olefin Lather Serial sulfonate Height Allrylbenzene Alkyl ether (Inches) ulionate Sulfate 40 0 O 7. 55 0 40 0 2. 000 0 40 2. 33 0 2O 20 9. 56 10 20 10 10. 81 20 10 1O 10. 87

Compositions e and 1 were according to the invention, the others beingincluded for comparison. Both e and f had better lather power than wasprovided by the best binary mixture of alkyl benzene sulfonate and alkylether sulfate, composition d. Moreover, composition 1 had better latherpower than would be expected of a 1:1 mixture of half the detergentingredients of compositions a and d, which would have the same formula.

The compositions according to the invention had excellent detergentproperties.

In the compositions of the present invention, the ternary mixture may beused in any desired proportion. If the proportion is very small, forexample less than 10% by weight of the composition, then inconvenientlylarge amounts of the composition may have to be transported and used inorder to achieve a given amount of cleaning. If the proportion is verygreat, then there may not be sufficient place for all other desiredingredients of the composition (such as builder salts in the case ofsolid compositions), or it may be difiicult to achieve a stablecomposition (in the case of liquid compositions). Suitable proportionsof the ternary mixture will often be found to be within the range from10 to 60%, by weight of the composition. Proportions within the rangefrom 20 to 50% are preferred for liquid compositions.

What is claimed is:

1. A detergent composition consisting essentially of a synergisticternary mixture of (A) a straight chain monoolefin sulfonate having 12to 16 carbon atoms in the molecule, (B) an alkyl benzene sulfonatehaving an alkyl chain containing 10 to 18 carbon atoms and (C) an alkylether sulfate having the formula RO(C H O) SO M wherein R is an alkylchain of 10 to 18 carbon atoms, x is a value from 1 to about 5, thecation of said sulfonate compounds and the cation M of said sulfatecompound being selected from the group consisting of alkali metal,ammonium, magnesium and alkaline earth metal, the proportion of saidmono-olefin sulfonate being from about 5 to 75% of the ternary mixtureand to 65% of a mixture of said alkyl aryl sulfonate and said alkylether sulfate in a ratio of from 9:1 to 3 :7 by weight.

2. A detergent composition according to claim 1 wherein said mono-olefinsulfonate has chain length of 12 to 14 carbon atoms.

3. A detergent composition according to claim 1 wherein the alkylbenzene sulfonate has an alkyl chain of 12 to 16 carbon atoms.

4. A detergent composition according to claim 3 wherein the alkyl groupof the alkyl benzene sulfonate is derived from the group consisting oftetrapropylene, pentapropylene, and mixtures thereof.

5. A detergent composition according to claim 3 wherein the alkyl groupof the alkyl benzene sulfonate is a straight chain having 12 carbonatoms.

6. A detergent composition according to claim 1 wherein the alkyl ethersulfate has an alkyl chain of 12 to 14 carbon atoms and is derived fromcoconut alcohols.

7. A detergent composition according to claim 6 wherein the alkyl ethersulfate has the formula where Rrepresents an alkyl group having 12 to 14carbon atoms.

8. A detergent composition according to claim 1 wherein the proportionof said mono-olefin sulfonate is from 5 to 50% of the ternary mixtureand the ratio of said alkyl benzene sulfonate to said alkyl ethersulfate is from 85:15 to 1:1.

9. A detergent composition according to claim 1 which References CitedUNITED STATES PATENTS 2,061,617 11/1936 Downing et a1. 260-513 2,086,2157/1937 DeCroote 252338 2,846,402 8/1958 Lew 252-152 2,972,583 2/1961Hewitt 252-161 FOREIGN PATENTS 704,288 2/1954 Great Britain.

6 OTHER REFERENCES Chem. Ber., 97, #10, 2903-13 (October 1964); HigherMolecular Aliphatic Sulfonic Acids. I. Z-Hydroxy-l-n- AlkanesulfonicAcids, F. Pushel and Claus Kaiser.

Chem. Ber. 97, #10, 2917- (October 1964); Higher Molecular AliphaticSulfonic Acids. II. S-Hydroxy-l-n- Alkanesulfonic Acids and Their InnerEsters (1,3-Sultones). F. Puschel and Claus Kaiser.

Chem. Ber. 97, #10, 2926-33 (October 1964); Higher Molecular UnsaturatedSulfonic Acids and the Hydrolysis of 1,3-Alkanesultones. F. Puschel andClaus Kaiser.

Chem. Ber. 98, 735-742 (1965); Higher Molecular Aliphatic SulfonicAcids. IV. Sulfonation of Unbranclied Alpha-Olefins with S0 F. Puscheland Claus Kaiser.

Stupel, Manufacturing Chemist, Combination of Raw Materials ImprovesSynthetic Detergents, March 1952, pp. 99-102.

LEON D. ROSDOL, Primary Examiner.

S. E. DARDEN, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,332,876 July 25, 1967 Arthur Polden Walker It is certified that errorappears in the above identified patent and that said Letters Patent arehereby corrected as shown below:

Column 4, line 51, 65% should read 25% Signed and sealed this 14th dayof April 1970.

(SEAL) Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A SYNERGISTICTERNARY MIXTURE OF (A) A STRAIGHT CHAIN MONOOLEFIN SULFONATE HAVING 12TO 16 CARBON ATOMS IN THE MOLECULE, (B) AN ALKYL BENZENE SULFONATEHAVING AN ALKYL CHAIN CONTAINING 10 TO 18 CARBON ATOMS AND (C) AN ALKYLETHER SULFATE HAVING THE FORMULA R(C2H4O)XSO2M WHEREIN R IS AN ALKYLCHAIN OF 10 TO 18 CARBON ATOMS, X IS A VALUE FROM 1 TO ABOUT 5, THECATION OF SAID SULFONATE COMPOUNDS AND THE CATION M OF SAID SULFATECOMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL,AMMONIUM, MAGNESIUM AND ALKALINE EARTH METAL, THE PROPORTION OF SAIDMONO-OLEFIN SULFONATE BEING FROM ABOUT 5 TO 75% OF THE TERNARY MIXTUREAND 95 TO 65% OF A MIXTURE OF SAID ALKYL ARYL SULFONATE AND SAID ALKYLETHER SULFATE IN A RATIO OF FROM 9:1 TO 3:7 BY WEIGHT.